JP5032774B2 - Ink for recording and ink set, ink cartridge, ink recorded matter, ink jet recording apparatus and ink jet recording method - Google Patents

Description

  The present invention provides a recording ink and ink set that are free of clogging of the head during recording, have excellent ejection stability, and provide a high-quality image with good color tone not only on dedicated recording paper but also on plain paper, and The present invention relates to an ink cartridge, an ink record, an ink jet recording apparatus, and an ink jet recording method.

  Inkjet printers have been remarkably popular due to the advantages of low noise and low running cost, and color printers that can print on plain paper have come to the market. However, all required properties such as color reproducibility, durability, light resistance, image drying, character bleeding (feathering), color boundary bleeding (color bleed), double-sided printability, ejection stability, etc. It is very difficult to satisfy, and the ink to be used is selected from the characteristics that are given priority depending on the application.

  Inks used for ink jet recording generally contain water as a main component and contain a coloring agent and a wetting agent such as glycerin for the purpose of preventing clogging. As the colorant, a dye is used because of its excellent color developability and stability. However, the light resistance, water resistance, and the like of an image obtained using a dye-based ink are inferior. In this case, the water resistance is improved to some extent by the improvement of the ink jet recording paper having the ink absorbing layer, but the plain paper is not satisfactory.

  In recent years, in order to improve these problems, an ink in which a pigment such as an organic pigment or carbon black is dispersed in water or an aqueous medium instead of a dye has been studied. As a general method for preparing a pigment-dispersed ink, a dispersing agent is dissolved in an aqueous medium, and then pigment particles are added and sufficiently moistened, followed by high-speed stirring using a homogenizer, and a ball such as a bead mill or a ball mill. Examples thereof include a method of preparing a dispersion using a kneading and dispersing machine, a kneading and dispersing machine using a shearing force such as a roll mill, and an ultrasonic dispersing machine. For example, Patent Document 2 and Patent Document 3 propose a method for improving discharge stability by making organic pigments into fine particles having a particle diameter of 50 nm or less using a specific dispersant. Patent Document 4 proposes an inkjet ink using a specific organic pigment and an anionic dispersant.

  Ink jet recording inks generally have a pigment particle diameter of 50 to 150 nm in terms of volume average particle diameter. When larger than this, it will cause clogging of a nozzle, and when smaller than this, there exists a problem that storage stability will become very bad. There are various types of dispersants, from low molecular weight surfactants to high molecular weight polymer dispersants. Although the polymer dispersants are excellent in storage stability, the pigment particle size is 150 nm in volume average particle size. The low molecular weight dispersant has a problem in storage stability although it is possible to reduce the pigment to a volume average particle size of 50 to 100 nm. For example, Patent Literature 1 and Patent Literature 6 propose a method of adding a water-soluble polymer as a method for compensating for the lack of storage stability of such a low molecular weight dispersant.

  In addition, there are surface-modified pigment inks that can be stably dispersed by modifying the pigment particle surface with a carboxyl group, a carbonyl group, a sulfone group, a hydroxyl group, etc. to impart hydrophilicity. For example, as a black pigment ink, so-called surface-modified carbon black that can be stably dispersed by introducing a hydrophilic group on the surface of carbon black has been developed and put into practical use. Furthermore, color pigments that can be stably dispersed in color pigment-based inks have been developed. However, these surface-modified pigment inks have the disadvantage that they are poor in scratch resistance and water resistance on plain paper and exclusive glossy paper.

  Ink jet inks using so-called microcapsules or emulsion type dispersions in which pigment particles are coated with a resin have been proposed. Although the dispersion state is stable for a long time because the pigment is tightly covered with the resin and the instability of ejection has been improved, it is difficult to produce dispersed particles having a small particle size suitable for inkjet. There is a problem that the manufacturing process is complicated and the cost is high.

  In order to improve the reduction in the saturation of the printed image due to such a large dispersed particle size, for example, in Patent Document 7 and Patent Document 8, a fluorosurfactant is added to the ink so that the ink droplets are on the paper surface. After landing, an attempt has been made to improve the saturation by spreading more uniformly on the concentric circles so as to fill the gaps between the dots by the ink droplets.

In addition, when red is printed with magenta ink and yellow ink, a phenomenon occurs in which the color tone varies depending on the order of ink landing on the paper. This phenomenon appears remarkably in the ink jet system in which printing is performed by scanning the ink ejection head, since the landing order is reversed in the forward path and the backward path, and is not acceptable particularly in the high density region of the pigment ink. Similarly, when printing green with yellow ink and cyan ink and when printing blue with cyan ink and magenta ink, a bidirectional color difference occurs. On the other hand, conventionally, since the bidirectional printing has been limited, the printing speed has been reduced.
For this reason, in Patent Document 4, it is said that bidirectional color difference can be reduced by using ink having at least four different hues as color ink. However, in this proposal, red ink, green ink, and blue ink are not used, and the configuration of the ink set is different.

  In addition, when using yellow ink, magenta ink, and cyan ink to form secondary colors of red, green, and blue, all dots are not filled in the gradation that exceeds the total amount restriction, and the characters become gaps. It looks out of focus. In addition, the secondary color using yellow ink has a problem that since the visibility of yellow is low, the characters appear more sloppy and the character quality deteriorates. Also, when forming a secondary color, two types of ink are applied within the same dot in order to form one gradation, and the total droplet amount is 2 to express the same gradation as that of a single color ink. However, there is a problem that the number of gradations is reduced because gradations relating to the total amount regulation cannot be expressed.

  The red ink can be produced by simply mixing magenta ink and yellow ink. By using this mixed red ink, the bidirectional color difference, character quality, and gradation can be improved as compared to using two separate colors. However, there was no difference in the saturation between this mixed red ink and the case of using two different colors, and it was not possible to measure the expansion of the color reproduction range.

  Further, by using a single red pigment, the saturation can be further improved. In particular, a high-saturation red ink can be prepared for a diketopyrrolopyrrole red pigment (see Patent Document 5). Similarly, by using a single phthalocyanine-based green pigment for green ink, it is possible to achieve a color tone with higher saturation than when two colors are superimposed. However, the problem with inks using diketopyrrolopyrrole red pigments is that the tone gradually shifts to the yellow side as the image density is increased and the saturation is increased. This phenomenon appears remarkably from around 90% of the recording duty, and the hue change in a high density and high saturation region becomes large.

  Furthermore, a problem when using a single red pigment, green pigment, particularly diketopyrrolopyrrole red pigment, and phthalocyanine green pigment is that it is difficult to stably disperse in water. When employed as an inkjet ink, a small particle size of about 100 nm or less is required, and in order to maintain such a small particle size in a stable state for a long time, It is necessary to select in consideration of compatibility and compatibility with the water-soluble solvent to be added.

  Therefore, it is possible to stably disperse diketopyrrolopyrrole-based red pigments and phthalocyanine-based green pigments that are excellent in color development in water, and the properties do not change even after long-term storage. Currently, no suitable recording ink or ink set has been provided.

Japanese Patent No. 3625595 (Japanese Patent Laid-Open No. 9-263720) JP-A-9-263722 JP 2002-88286 A JP 2003-276300 A JP-A-8-239610 Japanese Patent No. 3618493 JP 2003-268274 A JP 2003-335987 A

This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can stably disperse diketopyrrolopyrrole red pigments and phthalocyanine green pigments, which are excellent in color development, in water, and the physical properties do not change even after long-term storage, and the ejection stability by inkjet is excellent. It is an object of the present invention to provide a recording ink and ink set suitable as red ink or green ink, and an ink cartridge, an ink recorded matter, an ink jet recording apparatus, and an ink jet recording method using these.
In addition, the present invention can correct the deterioration of the character quality and the gradation when the secondary color is used, improve the printing speed by eliminating the bidirectional color difference, and use a single red pigment. Another object of the present invention is to provide a recording ink and ink set having a wide color reproduction range in which hue does not change depending on the amount of adhesion and high saturation, and an ink cartridge, an ink recorded matter, an ink jet recording apparatus and an ink jet recording method using these.

Means for solving the problems are as follows. That is,
<1> It contains at least a pigment, a dispersant, a water-soluble solvent, a penetrating agent, and water,
The recording ink is characterized in that the pigment contains at least one of a diketopyrrolopyrrole red pigment and a phthalocyanine green pigment.
<2> Diketopyrrolopyrrole red pigment is C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264 and C.I. I. The recording ink according to <1>, which is at least one selected from CI Pigment Red 272.
<3> The phthalocyanine green pigment is C.I. I. Pigment green 7 and C.I. I. The recording ink according to any one of <1> to <2>, which is at least one of pigment green 36.
<4> The dispersant according to any one of <1> to <3>, wherein the dispersant is at least one of a compound represented by the following structural formula (11) and a compound represented by the following structural formula (12). It is a recording ink.
^{_{A 1 -O- (CH 2 CH 2}} O) k -SO 3 M 1 ··· structural formula (11)
However, the structural formula (11), A ¹ is branched optionally also an alkyl group having 8 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a benzyl group, styrenated phenol group, distyrenated phenol group , And a β-naphthyl group. k represents an integer of 5 to 30. M ¹ represents any ^one of an alkali metal, ammonium, phosphonium, and alkanolamine.
^{_{A 1 -O- (CH 2 CH 2}} O) i -H ··· structural formula (12)
However, the structural formula (12), A ¹ is branched optionally also an alkyl group having 8 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a benzyl group, styrenated phenol group, distyrenated phenol group , And a β-naphthyl group. i represents an integer of 20 to 60.
<5> The recording ink according to any one of <1> to <4>, wherein the addition amount of the dispersant is 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
<6> An aqueous solution or dispersion of at least one of an acrylic resin, a methacrylic resin, a polyurethane resin, and a polyester resin, the resin having a mass average molecular weight of 5,000 to 100,000, and The recording ink according to any one of <1> to <5>, wherein the acid value is 50 to 200 KOHmg / g.
<7> The mass (X) of the dispersant in the recording ink and the mass (Y) of the solid content of the aqueous solution or dispersion of at least one of acrylic resin, methacrylic resin, polyurethane resin, and polyester resin. Is the recording ink according to any one of <1> to <6>, which satisfies the following formula: Y / X ≦ 1.
<8> The recording ink according to any one of <1> to <7>, wherein the penetrant includes any of a polyol compound having 8 to 11 carbon atoms and a glycol ether compound.
<9> The water-soluble solvent is glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol. The recording ink according to any one of <1> to <8>, wherein the recording ink is at least one selected from dipropylene glycol, and trimethylolpropane.
<10> A fluorosurfactant is contained, and the fluorosurfactant is at least one of perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, and perfluoroalkyl betaine. The recording ink according to any one of <1> to <9>.
<11> Polymer fine particles are contained, the volume average particle diameter of the polymer fine particles is 5 to 200 nm, and the polymer fine particles have a film-forming property after printing on a recording medium, and the minimum film-forming temperature is 30 ° C. or less. The recording ink according to any one of <1> to <10>.
<12> In an ink set including at least the recording ink according to any one of <1> to <11>,
When recording red with a recording duty of 90% or more, when using red ink with a recording duty of 90% or more and magenta ink with a recording duty of less than 10%, and recording red with a recording duty of less than 90% An ink set comprising a combination of red ink having a recording duty of 90% or more and yellow ink having a recording duty of less than 10%.
<13> An ink cartridge comprising the recording ink according to any one of <1> to <11> contained in a container.
<14> An ink jet comprising at least ink flying means for recording an image by applying a stimulus to the recording ink according to any one of <1> to <11> and causing the recording ink to fly. It is a recording device.
<15> The inkjet recording apparatus according to <14>, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.
<16> An inkjet including at least an ink flying step of recording an image by applying a stimulus to the recording ink according to any one of <1> to <11> and causing the recording ink to fly. It is a recording method.
<17> An inkjet recording method comprising at least an ink flying step of recording an image by applying a stimulus to each ink in the ink set according to <12> and causing each ink in the ink set to fly. is there.
<18> The inkjet recording method according to any one of <16> to <17>, wherein the stimulus is at least one selected from heat, pressure, vibration, and light.
<19> When recording red with a recording duty of 90% or more, red ink with a recording duty of 90% or more and magenta ink with a recording duty of less than 10% are used in combination, and red with a recording duty of less than 90% is recorded. In this case, the inkjet recording method according to any one of <16> to <18>, wherein a red ink having a recording duty of 90% or more and a yellow ink having a recording duty of less than 10% are used in combination.
<20> An ink recorded matter comprising an image recorded on a recording medium using the recording ink according to any one of <1> to <11>.

The recording ink of the present invention comprises at least a pigment, a dispersant, a water-soluble solvent, a penetrant, and water.
The pigment contains at least one of a diketopyrrolopyrrole red pigment and a phthalocyanine green pigment. According to the present invention, it is possible to stably disperse a diketopyrrolopyrrole red pigment or a phthalocyanine green pigment excellent in color development in an aqueous system, the physical properties do not change even after long-term storage, and excellent red ink ejection stability by inkjet Recording ink such as green ink can be provided.

  The ink cartridge of the present invention comprises the recording ink of the present invention contained in a container. The ink cartridge is suitably used for a printer using an ink jet recording method. When recording is performed using the ink stored in the ink cartridge, the head is not clogged during recording, the ejection stability is excellent, and a high-quality image with good color tone is obtained not only on the dedicated recording paper but also on plain paper. can get.

  The ink jet recording apparatus of the present invention has at least ink flying means for recording an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly. In the ink jet recording apparatus, the ink flying means applies energy to the recording ink of the present invention and causes the recording ink to fly to form an image. As a result, it is possible to correct the deterioration of character quality and gradation when using a secondary color, and improve the printing speed by eliminating bidirectional color difference. Therefore, it is possible to form an image with a wide color reproduction range where the hue does not change and a high saturation.

In the first embodiment, the ink jet recording method of the present invention comprises at least an ink flying step of recording an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly.
In the second embodiment, the ink jet recording method of the present invention comprises at least an ink flying step of recording an image by applying a stimulus to each ink in the ink set of the present invention and causing each ink in the ink set to fly. .
In the ink jet recording methods according to the first and second embodiments, it is possible to correct the deterioration of the character quality and the gradation when the secondary color is used, and to improve the printing speed by eliminating the bidirectional color difference. As a result, even when a single red pigment is used, an image with a wide color reproduction range in which the hue does not change depending on the amount of adhesion can be recorded.

  The ink recorded matter of the present invention has an image recorded on the recording medium using the recording ink of the present invention. In the ink recorded matter, a high image quality with a good color tone is maintained on the recording medium.

  According to the present invention, diketopyrrolopyrrole-based red pigments and phthalocyanine-based green pigments, which can solve various problems in the past and have excellent color development properties, can be stably dispersed in water, and the physical properties do not change even after long-term storage. A recording ink and ink set suitable as a red ink or green ink excellent in stability, and an ink cartridge, an ink record, an ink jet recording apparatus, and an ink jet recording method using the recording ink can be provided.

(Ink for recording)
The recording ink of the present invention contains at least a pigment, a dispersant, a water-soluble solvent, a penetrating agent, and water. Depending on the case, it contains other components.

-Pigment-
The pigment includes at least one of a diketopyrrolopyrrole red pigment and a phthalocyanine green pigment, and further includes other pigments as necessary.
Examples of the diketopyrrolopyrrole red pigment include C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264 and C.I. I. At least one selected from Pigment Red 272 is preferred.
Examples of the phthalocyanine green pigment include C.I. I. Pigment green 7 and C.I. I. At least one of the pigment green 36 is preferable.

The other pigment is not particularly limited and may be appropriately selected according to the purpose. For example, as the black pigment, for example, carbon black (such as furnace black, lamp black, acetylene black, channel black) ( CI pigment black 7), copper, iron (CI pigment black 11), metals such as titanium oxide, organic pigments such as aniline black (CI pigment black 1), and the like. .
The black pigment is preferably carbon black. This carbon black is excellent in color tone, is excellent in water resistance, light repellency and dispersion stability, and is inexpensive.

  Examples of the color are C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51; C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, and the like.

Of these pigments, those having good affinity with water are preferably used.
Other pigments (for example, carbon) are treated with resin, etc. to make them dispersible in water, and pigments (for example, carbon) surfaces are added with functional groups such as sulfone groups and carboxyl groups and dispersed in water. Processed pigments made possible can be used.
Further, the pigment may be included in the microcapsule so that the pigment can be dispersed in water.

  The volume average particle diameter of the pigment is preferably 20 to 200 nm, more preferably 50 to 150 nm in the recording ink. The content of the dispersed fine particles in the ink is preferably about 2 to 20% by mass, more preferably 4 to 15% by mass, based on the solid content of the pigment and the dispersant combined.

  There is no restriction | limiting in particular as content in the said recording ink of the said pigment, According to the objective, it can select suitably, 0.5-25 mass% is preferable, and 2-15 mass% is more preferable. If the content is less than 0.5% by mass, the image density may be low and the image may have no contrast. If the content exceeds 25% by mass, it is difficult to ensure the dispersion stability of the colorant. The nozzles and the like are easily clogged, and the reliability may be deteriorated.

-Dispersant-
The dispersant is not particularly limited and can be appropriately selected from dispersants used in preparing the pigment dispersion according to the purpose. For example, polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile co-polymer Polymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer Polymer, stin-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid copolymer-acrylic acid alkyl ester copolymer, Styrene-maleic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinegar Vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer, And compounds represented by 11) and (12). These dispersing agents may be used individually by 1 type, and may use 2 or more types together.
^{_{A 1 -O- (CH 2 CH 2}} O) k -SO 3 M 1 ··· structural formula (11)
However, the structural formula (11), A ¹ is branched optionally also an alkyl group having 8 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a benzyl group, styrenated phenol group, distyrenated phenol group , And a β-naphthyl group. k represents an integer of 5 to 30. M ¹ represents any ^one of an alkali metal, ammonium, phosphonium, and alkanolamine.
^{_{A 1 -O- (CH 2 CH 2}} O) i -H ··· structural formula (12)
However, the structural formula (12), A ¹ is branched optionally also an alkyl group having 8 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a benzyl group, styrenated phenol group, distyrenated phenol group , And a β-naphthyl group. i represents an integer of 20 to 60.

  Among these, it is preferable to use any of the compounds represented by the structural formulas (11) and (12).

Examples of the compound represented by the structural formula (11) include a compound represented by the following structural formula (1), and more specifically, a compound represented by the structural formula (A) is preferable.
In the structural formula (1), R ¹ represents any of an alkyl group having 1 to 12 carbon atoms which may be branched, a benzyl group, a styryl group, and a distyryl group. R ² represents any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be branched, a benzyl group, and a styryl group. j represents an integer of 5 to 20. M ¹ represents any ^one of an alkali metal, ammonium, phosphonium, and alkanolamine.

Examples of the compound represented by the structural formula (12) include polyoxyethylene lauryl ether. Among these, compounds represented by the following structural formulas (13) and (13 ′) are preferable.
_{C 12 H 25 -O- (CH 2} CH 2 O) 43 H ··· structural formula (13)
_{C 12 H 25 -O- (CH 2} CH 2 O) 42 H ··· structural formula (13 ')

  1-100 mass parts is preferable with respect to 100 mass parts of said pigments, and, as for the addition amount of the said dispersing agent, 10-50 mass parts is more preferable. If the amount of the dispersant added is too small, the pigment may not be sufficiently fined. If the amount is too large, excess components not adsorbed on the pigment will affect the ink physical properties, causing image bleeding and water resistance. And deterioration of wear resistance.

-Water-soluble or water-dispersible resin-
Storage stability can be improved by adding an aqueous solution or dispersion of at least one of acrylic resin, methacrylic resin, polyurethane resin, and polyester resin to the recording ink of the present invention. These can be added together with a water-soluble solvent, a surfactant, etc. when dispersing the pigment using a dispersing device such as a bead mill or an attritor, or when preparing a recording ink. It is more preferable to add it.

The acrylic resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid- Acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, acrylic acid alkyl ester copolymer, Examples thereof include vinyl acetate-acrylic acid copolymer.
The methacrylic resin is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polymethacrylic acid, styrene-methacrylic acid copolymer, stin-methacrylic acid-acrylic acid alkyl ester copolymer, Examples include styrene-α-methylstyrene-acrylic acid copolymer.
The polyurethane resin is not particularly limited and may be appropriately selected depending on the purpose.For example, a resin solubilized in water by introducing a hydrophilic component such as a carboxyl group or a sulfone group into the urethane skeleton, Or what was disperse | distributed to water is mentioned.
As the polyurethane resin, commercially available ones may be used. For example, Hydran HW-970 and HW-940 manufactured by Dainippon Ink & Chemicals, Inc. Takelac W-6010 manufactured by Mitsui Takeda Chemical Co., Ltd. -6061, W-5025, Dai-ichi Kogyo Seiyaku Co., Ltd. SF-107M, SF-460, etc. are mentioned.
The polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyester resin is solubilized in water by introducing a hydrophilic group such as a carboxyl group or a sulfone group into the side chain of the polyester skeleton. And those dispersed in water.
As said polyester resin, you may use what is marketed, for example, Takamatsu Oil Co., Ltd. Besresin A-210, A-520, A-620 etc. are mentioned.

The mass average molecular weight of these resins is preferably 5,000 to 100,000, and more preferably 10,000 to 30,000. If the mass average molecular weight exceeds 100,000, the viscosity of the recording ink becomes high and ejection from the ink jet nozzle may become unstable. If it is less than 5,000, the effect on storage stability is lost. Therefore, it is not preferable.
Here, the mass average molecular weight of the resin can be measured by GPC (gel permeation chromatography).

  In the recording ink of the present invention, acrylic resin, methacrylic resin, polyurethane resin, polyester resin, a water-soluble substance of these resins, and a mass (Y) of a solid content of an aqueous dispersion of these resins, and a mass of the dispersant The relationship with (X) is preferably Y / X ≦ 1, and more preferably Y / X ≦ 0.01 to 0.5. When the Y / X value is greater than 1, the viscosity of the ink becomes high, which may cause a problem during ink ejection.

-Water-soluble solvent-
The recording ink of the present invention uses water as a liquid medium, but the following water-soluble solvents are used for the purpose of preventing the ink from drying and for improving the dispersion stability. . These are excellent in solubility and prevention of poor jetting characteristics due to water evaporation.

  The water-soluble solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, Examples include amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other water-soluble solvents. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyhydric alcohols include glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, and trimethylolethane. , Ethylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2 , 4-butanetriol, 1,2,3-butanetriol, petriol and the like.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like. Can be mentioned.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, Etc.
Examples of the amides include formamide, N-methylformamide, N, N-dimethylformamide, and the like.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and the like.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.
The other water-soluble solvent preferably contains sugar. Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose. Further, the derivatives of these saccharides are represented by the reducing sugars of the saccharides described above (for example, sugar alcohol (general formula: HOCH ₂ (CHOH) nCH ₂ OH (where n = 2 to 5 represents an integer)). ), Oxidized sugars (for example, aldonic acid, uronic acid, etc.), amino acids, thioic acids, etc. Among these, sugar alcohols are preferred, and specific examples include maltitol, sorbit and the like.
Among these water-soluble solvents, glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, Dipropylene glycol and trimethylolpropane are particularly preferred from the viewpoints of storage stability and ejection stability.
The mass ratio of the pigment and the water-soluble solvent has a great influence on the stability of ink ejection from the head. If the blending amount of the wetting agent is small even though the pigment solid content is high, water evaporation near the ink meniscus of the nozzle may progress and cause ejection failure.

  The content of the water-soluble solvent in the recording ink is preferably 10 to 50% by mass, and more preferably 15 to 35% by mass. The ratio of the solid content of the pigment particles including the water-soluble solvent and the dispersant is preferably 0.67 to 12.5, more preferably 1.0 to 6.0, and still more preferably 2.0 to 4.0. Recording inks in this range have very good drying, storage and reliability tests.

-Penetration agent-
As the penetrant, a polyol compound having 8 to 11 carbon atoms or a glycol ether compound is suitable.

Examples of the polyol compound having 8 to 11 carbon atoms include 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, and 2,2,4-trimethyl-1,3-pentane. Examples include diols. Among these, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol are particularly preferable.
Examples of the glycol ether compound include polyhydric alcohol alkyl ether compounds and polyhydric alcohol aryl ether compounds.
Examples of the polyhydric alcohol alkyl ether compound include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. .
Examples of the polyhydric alcohol aryl ether compound include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
The content of the penetrant in the recording ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 to 4% by mass.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, anionic surfactants and nonionic surfactants are preferred, and among these, fluorine surfactants are more preferred. preferable. A surfactant that does not impair the dispersion stability is selected depending on the combination of the color material, the wetting agent, and the water-soluble organic solvent.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
Examples of the nonionic surfactant include acetylene glycol surfactants, polyols, glycol ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, Examples thereof include oxyethylene alkylamine, polyoxyethylene alkylamide, and acetylene glycol.
Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyn-3-ol, a compound represented by the following structural formula (7), and the like.
Examples of commercially available acetylene glycol surfactants include Surfynol 104, 82, 465, 485, and TG manufactured by Air Products (USA). Among these, Surfynol 465, 104 can be used. And TG are particularly preferable because they exhibit good print quality.

As the anionic surfactant and nonionic surfactant, for example, those represented by the following structural formulas (2) to (7) are preferable.
^{_{R 3 -O- (CH 2 CH 2}} O) h CH 2 COOM ··· structural formula (2)
In the structural formula (2), R ³ represents an alkyl group, and an alkyl group having 6 to 14 carbon atoms which may be branched is preferable. h represents an integer of 3 to 12. M represents one selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.
In the structural formula (3), R ⁴ represents an alkyl group and represents an optionally branched alkyl group having 5 to 16 carbon atoms. M represents one selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

In the Structural Formula (4), R ³ represents a hydrocarbon group, for example, such as an alkyl group branched carbon atoms and optionally 6-14. k represents an integer of 5 to 20.

However, R ⁵ represents a hydrocarbon group in the structural formulas (5) and (5 ′). L, m, n, and p each represent an integer of 1-20. As said hydrocarbon group, the C6-C14 alkyl group which may be branched is mentioned.

However, in the structural formulas (6) and (6 ′), R ⁶ represents a hydrocarbon group. L, m, n, and p represent an integer of 1-20. As said hydrocarbon group, the C6-C14 alkyl group which may be branched is mentioned.

However, q and r represent the integer of 0-40 in the said Structural formula (7).

The fluorosurfactant is not particularly limited, and examples thereof include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, and perfluoroalkyl betaine. , Perfluoroalkylamine oxide, and perfluoroalkyl ether compounds.
As the fluorine-based compound, commercially available compounds may be used. For example, Surflon S-111, S-112, S-113, S121, S131, S132, S-141, S-145 (all Asahi Glass Co., Ltd.), Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M), MegaFuck F- 470, F1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont) FT-110, 250, 251, 400S (all manufactured by Neos Co., Ltd.) and the like. Among these, FT-110, 250, 251 and 400S (all manufactured by Neos Co., Ltd.) are preferable because good print quality, particularly color developability and leveling property on paper are remarkably improved.
When the fluorosurfactant is used in the recording ink of the present invention, the surface tension of the recording ink is further reduced, and penetration into the recording medium after the ink droplets have landed on the recording medium such as paper is accelerated. Therefore, it is possible to easily penetrate between the agglomerated particles in the recording ink, and the agglomerated particles are separated to prevent agglomeration and color bleeding. it is conceivable that.

-Polymer particles-
The recording ink of the present invention contains polymer particles having a volume average particle diameter of 5 to 200 nm, the polymer particles have film-forming properties after printing on a recording medium, and have a minimum film-forming temperature of 30 ° C. or lower. Preferably there is.
The film-forming property of the polymer particles means that when polymer particles are dispersed in water to form an emulsion, a resin film is formed when water in the aqueous emulsion is evaporated.
The ink composition to which the polymer particles are added forms a film when the volatile components are evaporated, and can firmly fix the coloring material pigment content in the ink to the recording medium. It is possible to form an image having excellent properties.
Since the ink composition to which the polymer particles are added forms a film at room temperature, the minimum film forming temperature of the polymer particles is preferably 30 ° C. or less, and more preferably 10 ° C. or less.
The minimum film forming temperature can be measured according to ISO 2115 or ASTM D2354.
The average particle diameter of the polymer particles is preferably 5 to 200 nm, and more preferably 10 to 100 nm.
The polymer particles are not particularly limited and can be obtained by a known method. For example, an emulsion polymerization of an unsaturated vinyl monomer (unsaturated vinyl monomer) in water in which a polymerization catalyst and an emulsifier are present, etc. Is mentioned.
The content of the polymer particles is preferably 0.5 to 20.0% by mass and more preferably 1.0 to 5.0% by mass with respect to the total amount of the recording ink. When the content of the polymer particles is less than 0.5% by mass, there is a possibility that sufficient scratch resistance and water resistance may not be obtained. In some cases, the components may stick, ink ejection becomes unstable, and nozzle clogging may occur.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected according to need. Examples include chelating reagents, oxygen absorbers, and light stabilizers.

  There is no restriction | limiting in particular as said antifoamer, According to the objective, it can select suitably, For example, a silicone type antifoamer, a polyether antifoamer, a fatty acid ester antifoamer etc. are mentioned suitably. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone type antifoaming agent is preferable at the point which is excellent in the bubble-breaking effect.

  Examples of the silicone-based antifoaming agent include an oil-type silicone-based antifoaming agent, a compound-type silicone-based antifoaming agent, a self-emulsifying silicone-based antifoaming agent, an emulsion-type silicone-based antifoaming agent, and a modified silicone-based antifoaming agent. , Etc. Examples of the modified silicone-based antifoaming agent include amino-modified silicone antifoaming agents, carbinol-modified silicone antifoaming agents, methacrylic-modified silicone antifoaming agents, polyether-modified silicone antifoaming agents, alkyl-modified silicone antifoaming agents, and higher grades. Examples include fatty acid ester-modified silicone antifoaming agents and alkylene oxide-modified silicone antifoaming agents. Among these, the self-emulsifying silicone-based antifoaming agent and the emulsion-type silicone-based antifoaming agent are preferable in consideration of use in the recording ink that is an aqueous medium.

  Commercially available products may be used as the antifoaming agent, such as silicone-based antifoaming agents (KS508, KS531, KM72, KM85, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd. silicone antifoam (Q2183A, SH5510, etc.), Nippon Unicar Co., Ltd. silicone antifoam (SAG30 etc.), Asahi Denka Kogyo Co., Ltd. Nate series).

There is no restriction | limiting in particular as content in the said recording ink of the said defoamer, According to the objective, it can select suitably, For example, 0.001-3 mass% is preferable, 0.005-0.5 The mass% is more preferable.
When the antifoaming agent is contained in the recording ink, it is particularly excellent in storage stability and ejection stability over time, and when the content is less than 0.001% by mass, the content effect is not sufficient. If the amount exceeds 3% by mass, clogging is likely to occur, and the reliability of the recording ink may be deteriorated.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

The pH adjusting agent can stabilize the dispersion state by keeping the ink alkaline, and can stabilize ejection. In addition, when the pH is 11 or more, the amount of the material for the ink jet head and the ink supply unit to be melted is large, and problems such as ink quality change, leakage, and ejection failure occur. It is more preferable to add the pH adjusting agent when kneading and dispersing the pigment in water together with the dispersing agent than after adding the kneading and dispersing with additives such as a wetting agent and a penetrating agent. This is because dispersion may be destroyed by adding some pH adjusters.
Examples of the pH adjuster include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol and the like as alcohol amines. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium hydroxide. Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like.

Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenolic antioxidants (including hindered phenolic antioxidants) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-Butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.
Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate] methane, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and the like.
Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl β. , β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, trinonylphenyl phosphite, and the like.

Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate-based ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of the nickel complex-based ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), and 2,2′-thiobis. (4-tert-octyl ferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octyl ferrate) triethanolamine nickel (II), and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  The recording ink of the present invention includes at least one of a diketopyrrolopyrrole red pigment and a phthalocyanine green pigment, a dispersant, a water-soluble solvent, and any of a polyol compound having 8 to 11 carbon atoms and a glycol ether compound, Water and other components as necessary are dispersed or dissolved in an aqueous medium, and further stirred and mixed as necessary. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

  There is no restriction | limiting in particular as coloring of the recording ink of this invention, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

Although there is no restriction | limiting in particular as the physical property of the recording ink of this invention, For example, it is preferable that surface tension, a viscosity, electrical conductivity, pH, etc. are the following ranges.
The surface tension is preferably 35 mN / m or less at 20 ° C.
The viscosity is preferably 2 to 20 mPa · s at 25 ° C., more preferably 3 to 10 mPa · s. If the viscosity is less than 2 mPa · s, bleeding may occur in the image, and if it exceeds 20 mPa · s, it may be difficult to ensure ejection stability.
As said electrical conductivity, 0.5 S / m or less is preferable, for example, and 0.005-0.4 S / m is more preferable.
As said pH, 7-11 are preferable, for example.

(Ink set)
The ink set of the present invention includes at least the recording ink of the present invention, and is a combination of at least one of yellow ink, magenta ink, cyan ink, and black ink.
Any of the yellow ink, magenta ink, cyan ink, and black ink is not particularly limited and may be appropriately selected depending on the purpose.
In the ink set, when recording red with a recording duty of 90% or more, red ink with a recording duty of 90% or more and magenta ink with a recording duty of less than 10% are used in combination, and red with a recording duty of less than 90% is used. When recording, it is preferable to use red ink having a recording duty of 90% or more and yellow ink having a recording duty of less than 10% in combination.
Here, the recording duty refers to the ratio of the color material provided in the unit recording area, and is 100% at the maximum for the temporary color and 200% at the maximum for the secondary color. Details of the recording duty will be described later.

  The recording ink of the present invention uses an piezoelectric head as a pressure generating means for pressurizing ink in an ink flow path as an ink jet head, and deforms a diaphragm that forms the wall surface of the ink flow path to increase the volume in the ink flow path. A so-called piezo type that discharges ink droplets by changing (refer to Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor. (Refer to Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms the wall surface of an ink flow path and an electrode are arranged opposite to each other, and the diaphragm is deformed by an electrostatic force generated between the diaphragm and the electrode. Therefore, a printer equipped with any inkjet head such as an electrostatic type (see Japanese Patent Application Laid-Open No. 6-71882) that discharges ink droplets by changing the volume in the ink flow path. Can also be used well.

  The recording ink of the present invention can be suitably used in various fields, and can be suitably used in an image forming apparatus (printer or the like) based on an ink jet recording method. The recording ink is heated at 50 to 200 ° C. and can be used for a printer or the like having a function of accelerating print fixing. The following ink cartridge, ink recorded matter, ink jet recording apparatus, and ink jet recording method of the present invention It can be particularly preferably used.

(ink cartridge)
The ink cartridge of the present invention contains the recording ink of the present invention in a container, and further includes other members and the like appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 shows an external perspective view of the ink cartridge before loading into the ink jet recording apparatus, and FIG. 2 shows a front sectional view of the ink cartridge.
As shown in FIG. 2, the ink cartridge 7 includes an ink absorber 42 that absorbs ink of a desired color in a cartridge main body 41. The cartridge body 41 is formed by adhering or welding the upper lid member 44 to the upper opening of the case 43 having a wide opening at the upper portion, and is made of, for example, a resin molded product. The ink absorber 42 is made of a porous material such as a urethane foam, and after being compressed and inserted into the cartridge body 41, the ink is absorbed.

  An ink supply port 45 for supplying ink to the recording head 6 is formed at the bottom of the case 43 of the cartridge body 41, and a seal ring 46 is fitted on the inner peripheral surface of the ink supply port 45. The upper lid member 44 has an air opening 47 formed therein. In the cartridge main body 41, the case 43 is compressed and deformed by the pressure applied to the wide side wall when the ink supply port 45 is closed and when the cartridge is handled during loading or transportation, or during vacuum packaging. In order to prevent internal ink from leaking, a cap member 50 is attached.

Further, as shown in FIG. 1, the atmosphere opening 47 is sealed by sticking a film-like sealing member 55 having an oxygen permeability of 100 ml / m ² or more to the upper lid member 44. In this way, by sealing the air opening 47 with the sealing member 55 having an oxygen permeability of 100 ml / m ² or more, the ink cartridge 7 is packaged under reduced pressure using a packaging member such as a non-permeable aluminum laminate film. Thus, even when the gas is dissolved in the ink due to the atmosphere in the space A (see FIG. 2) generated between the ink absorber 42 and the cartridge main body 41 when the ink is filled, the ink is passed through the seal member 55. The air inside is discharged into the space between the packaging body outside the cartridge main body 41 with a high degree of vacuum, and the degree of deaeration of the ink is improved.

  The ink cartridge of the present invention contains the recording ink (ink set) of the present invention and can be used by being detachably attached to various ink jet recording apparatuses, and can be attached to and detached from the ink jet recording apparatus of the present invention described later. It is particularly preferable to install and use it.

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The ink jet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of forming an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly.
The ink flying means is means for forming an image by applying a stimulus to the recording ink of the present invention and causing the recording ink to fly. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.

  The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, Examples include thermal actuators that use phase change due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, electrostatic actuators that use electrostatic force, etc. It is done.

  There are no particular restrictions on the manner in which the recording ink flies, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the recording ink in the recording head. Corresponding thermal energy is applied using, for example, a thermal head, bubbles are generated in the recording ink by the thermal energy, and the recording ink is formed into droplets from the nozzle holes of the recording head by the pressure of the bubbles. And a method of discharging and jetting. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And the recording ink is ejected and ejected as droplets from the nozzle holes of the recording head.

The size of the recording ink droplets to be ejected is preferably 3 to 40 pl, for example, and the ejection jet speed is preferably 5 to 20 m / s, and the driving thereof. The frequency is preferably 1 kHz or more, and the resolution is preferably 300 dpi or more.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

Next, in the present invention, the scanning direction at the time of recording can be determined according to the duty of the image data.
In order to perform full color recording in an ink jet recording apparatus that forms an image using four colors of ink, the ink droplets of these four colors are landed on a recording medium with an appropriate balance, and other colors are mixed while being mixed. I will create it. Here, when recording a green (G) image, cyan (C) and yellow (Y) are mixed and recorded. That is, C and Y dots are placed on the same pixel.

FIGS. 5A and 5B show the state of ink droplets that have landed when ink droplets are ejected onto plain paper using the recording head. FIG. 5A is a cross-sectional view of plain paper during forward recording (in order of C → Y), and FIG. 5B is a cross-sectional view of plain paper during backward recording (in order of Y → C). In FIG. 5A, C recorded earlier covers the surface, and Y recorded later penetrates deeper than C.
On the other hand, in FIG. 5B, Y recorded earlier covers the surface, and C recorded later penetrates deeper than Y. When these recorded materials are viewed from the surface, (a) looks more cyanish green and (b) looks more yellowish green. For this reason, even in the case of the same CY color mixture, in the case of reciprocal recording, the color becomes completely different, and color unevenness occurs alternately for each line feed as shown in FIG.

In general, it is said that the level at which a human can feel the color difference ΔE * represented by the following equation in an adjacent image is approximately 1.0.
From FIG. 7, it can be said that the color difference tends to increase as the recording duty increases for R, B, and G. For the duty that the color difference ΔE * is 1.0 or more, R is approximately 75% and G is approximately 35%. , B is a high concentration region of about 57%.
In other words, eliminating bidirectional color difference without reducing the printing speed as much as possible means that one-way printing is performed in a high-duty recording area where the color difference is conspicuous and bidirectional printing is performed in a low-duty recording area where the color difference is not conspicuous. Can be achieved. For example, one-way printing is performed at a duty of 75% or more and bidirectional printing is performed at a duty of 75% or less, so that both high-speed printing and bidirectional color difference elimination can be effectively achieved. Since this threshold varies depending on the ink composition, color material, and the like, it is preferable to set the threshold appropriately for each model.

  Whether or not the bi-directional color difference is conspicuous is actually determined by the color difference near the boundary of scanning rather than the average color difference of the whole. This is due to human visual characteristics and is sensitive to the color difference between adjacent areas, but is insensitive to the color difference at a slightly distant place. Therefore, it is preferable to detect the boundary area of scanning and other areas separately to determine whether the scanning is bidirectional or unidirectional.

FIG. 8A shows a method for calculating the recording duty of a predetermined area of image data in an image area (scanning area: also referred to as 1 band) of the scanning width of the recording head to be recorded × 300 dots (recording width of the recording head). Here, a case where two windows are used as a plurality of windows is shown. A window B62 for calculating the duty in the vicinity of the boundary of the image area (boundary between different bands) is prepared, and the recording duty in the window is calculated from the image data in this window while scanning the window in the image area. To do.
The window A61 is for calculating the recording duty (duty over the entire width of the image area in the recording medium conveyance direction) over the entire recording width of the recording head with the size of the horizontal resolution (600 dots per inch = 600 dpi). In this embodiment, the window has a size of 300 dots long × 128 dots wide.
Window B is used to calculate the recording duty of an area close to the boundary of the image area to be recorded by each scan (boundary with the adjacent band). In this embodiment, the window has a size of 32 dots vertically × 128 dots horizontally. It is said.

As for the position and size of the window, in the case of the window B62, it may be set to a position where the recording duty is read in the vicinity of the end of the band, that is, in the vicinity of the boundary between the bands. Any range that reads the recording duty in the range on the boundary 63 side from the position is desirable. Further, it is desirable to set the position so that the boundary 63 includes the recording duty of the nearest dot, but the position may be set by removing several dots from the boundary 63.
In the case of the window A61, it is desirable that the window has a width that can read the duty of the entire width (bandwidth) in the direction orthogonal to the scanning direction of the head, but it is sufficient if the recording duty of the bandwidth is reflected. The position may be set by removing several dots from 63.
Further, the lengths of the windows A and B in the head scanning direction (band length direction) are set to 128 dots, but the length is not limited to this, and any length can be used as long as the recording duty of the window can be easily calculated.

In the above-described windows A and B, the number of image data to be calculated in each window is different in this embodiment. In window A, calculation is performed with a relatively large number of image data in order to capture the average density distribution in the scanning region, and in window B, relative density is used in order to capture the local density distribution in the boundary portion. The calculation is performed with a small number of image data.
However, this point can also be obtained by specifying the window at a position that reflects the boundary and the bandwidth as described above. Therefore, the window does not necessarily have the relationship of the number of image data as in the present embodiment. May be.
The calculation of the recording duty in these windows is performed using image data stored in the buffer of the recording control unit.

As a window scanning method, as shown in FIG. 8B, a scanning method in which each window is shifted by one line unit in the scanning direction (band length direction) of the recording head to calculate the recording duty, or FIG. As shown in FIG. 6, a scanning method may be used in which the recording duty is calculated by shifting each window length in the band length direction (each 128 dots in the horizontal direction in this embodiment).
The recording duty Dc of the cyan image in the window, the recording duty Dm of the magenta image, and the recording duty Dy of the yellow image are counted, and the summed Dc + Dm + Dy is set as the recording duty in the window at a certain window position.

In this embodiment, the recording duty threshold value of each window is set to 100% for window A and 75% for window B. Here, the recording duty of 100% is defined as the case where there is one dot of color ink recorded at a pixel position of 1/600 inch × 1/600 inch. Therefore, for example, a 100% cyan image means that the area is filled with cyan dots, and 200% is a blue solid image, for example, which is filled with cyan and magenta dots. Point to.
That is, the recording duty is the ratio of the color material applied in the unit recording area, and is 100% at the maximum for the temporary color and 200% at the maximum for the secondary color.

When the recording duty of window A at all positions in the recording area where recording is to be performed is 100% or less, and when the recording duty of window B at all positions is 75% or less, forward scanning and backward scanning are satisfied. If the recording speed is increased by performing recording in both directions (reciprocal recording), and either of the conditions is not satisfied, recording is performed unevenly by performing recording (one-way recording) in either forward scanning or backward scanning. We are trying to reduce it.
In this embodiment, the threshold value of the recording duty of window A is made smaller than the threshold value of window B. Since window B is the recording duty at the boundary, there is a tendency to be noticeable even if there is little unevenness. This is because if the threshold value of window A is made smaller and stricter, the ratio of one-way recording becomes too large and the recording speed is lowered.

FIG. 9 is a flowchart of the above operation. First, in step 1, recording is performed for the first scan (n = 1) of the recording head in accordance with the image data. In this embodiment, the scanning direction at this time starts from the home position side of the recording head. However, the scanning direction is not limited to this.
Subsequently, in step 2, n = n + 1 is set in order to move to the next scanning (second band recording).
In step 3, the recording duty of window A and window B at a position of the next scanning (for example, the second scanning) is calculated from the recording duty of each color. In step 4, whether the recording duty of window A is 100% or less. Is determined. When it is 100% or less, the process proceeds to Step 5, and when it exceeds 100%, the process proceeds to Step 7. If 100% or less, the process proceeds to step 5 to determine whether the recording duty of the window B is 75% or less. If 75% or less, the process proceeds to step 6; In step 6, the setting is made so as to perform recording in the direction opposite to the recording direction of the previous time (here, the first scan), that is, reciprocal recording. In step 7, a setting is made to perform recording in the same direction as the previous recording direction, that is, one-way recording.
After step 6, it is determined in step 8 whether each window has finished all the shifts in the n band. If not, the window is shifted to the next position in step 9. After the shift, the process returns to step 3 and reading calculation is performed to check whether there is a portion where the recording duty exceeds the reference value until the entire shift is completed.
If no window exceeds the reference value even after all the windows have been shifted, recording is performed in the direction opposite to the (n-1) th band (step 10).
When recording in the same direction as the previous band is set in step 7, recording is performed without calculating the recording duty of the next window in this embodiment.
The above operation is repeated until all recording is completed.

  Next, the recording ink of the present invention is accommodated in an ink cartridge with reference to the drawings, and the ink cartridge is mounted on an ink jet printer and ejected and ejected as droplets from a fine ejection port to form an image on a recording medium. How to do will be described.

FIG. 3 is a schematic front view of a mechanism part of a serial type ink jet recording apparatus on which an ink cartridge having an ink containing part containing the ink of the present invention is mounted.
The mechanism portion of this ink jet recording apparatus lays the main support guide rod 3 and the sub support guide rod 4 between the side plates 1 and 2 on both sides in a substantially horizontal positional relationship, and the main support guide rod 3 and the sub support guide. The carriage 4 is supported by the rod 4 so as to be slidable in the main scanning direction.

The carriage unit 5 has four heads 6 for ejecting yellow (Y) ink, magenta (M) ink, cyan (C) ink, and black (Bk) ink, respectively, and an ejection surface (nozzle surface) 6a. The four ink cartridges 7y, 7m, 7c, and 7k, which are ink supply bodies for each color, are mounted downward and are supplied to the four heads 6 on the upper side of the heads 6 of the carriage unit 5. Is installed in a replaceable manner.
The carriage unit 5 is connected to a timing belt 11 stretched between a driving pulley (drive timing pulley) 9 and a driven pulley (idler pulley) 10 that are rotated by the main scanning motor 8, and the main scanning motor 8 is connected to the carriage unit 5. By controlling the driving, the carriage 5, that is, the four heads 6 are moved in the main scanning direction.

  Further, the sub-frames 13 and 14 are erected on the bottom plate 12 connecting the side plates 1 and 2, and a conveyance roller 15 for feeding the paper 16 in the sub-scanning direction orthogonal to the main scanning direction is provided between the sub-frames 13 and 14. Holds freely. A sub-scanning motor 17 is disposed on the side of the sub-frame 14, and a gear 18 and a transport roller 15 fixed to the rotation shaft of the sub-scanning motor 17 in order to transmit the rotation of the sub-scan motor 17 to the transport roller 15. And a gear 19 fixed to the shaft.

  Further, between the side plate 1 and the sub-frame 12, a reliability maintenance / recovery mechanism (hereinafter also referred to as "sub-system") 21 of the head 6 is disposed. The sub-system 21 holds four cap means 22 for capping the ejection surface of each head 6 by a holder 23, and this holder 23 is held by a link member 24 so as to be swingable so that the carriage unit 5 can move in the main scanning direction. When the carriage unit 5 comes into contact with the engaging portion 25 provided on the holder 23 by the movement of the holder 23, the holder 23 is lifted up according to the movement of the carriage unit 5 and the ejection surface 6a of the inkjet head 6 is capped by the cap means 22, As the carriage unit 5 moves to the printing region side, the holder 23 is lifted down as the carriage unit 5 moves, so that the cap means 22 moves away from the ejection surface 6 a of the inkjet head 6.

The cap means 22 is connected to the suction pump 27 via the suction tube 26, forms an atmosphere opening port, and communicates with the atmosphere via the atmosphere opening tube and the atmosphere opening valve. The suction pump 27 discharges the sucked waste liquid to a waste liquid storage tank (not shown) through a drain tube or the like.
Further, on the side of the holder 23, a wiper blade 28, which is a wiping means made of an elastic member such as a fiber member, a foam member, or rubber, for wiping the discharge surface 6a of the inkjet head 6 is attached to a blade arm 29. Reference numeral 29 is pivotally supported so that it can be swung by rotation of a cam that is rotated by a driving means (not shown).

Next, FIG. 4 shows an example of the configuration of a recording cartridge (recording unit) provided with an ink containing portion containing the ink of the present invention and a head portion for ejecting ink droplets. The recording unit will be described below.
The recording unit 30 is of a serial type, and the main part is composed of a head 6, an ink tank 33 that stores ink supplied to the head 6, and a lid member 34 that seals the inside of the ink tank 33. The
A number of nozzles 32 for ejecting ink are formed in the head 6 of the recording unit 30. The ink is guided from the ink tank 33 to a common liquid chamber (not shown) via an ink supply pipe (not shown), and the nozzles according to an electric signal from the recording apparatus main body input from the electrode 31. 32 is discharged. Such a type of recording unit 30 has a structure suitable for a head of a type that can be manufactured at low cost, a so-called thermal type or bubble type head that uses thermal energy as a driving power source. Since the ink of the present invention uses an ink having excellent permeability in a recording method such as bubble or thermal method, the wettability to a thermal element is improved, ejection stability and frequency stability are obtained, and safety is achieved. It is highly suitable and very suitable.

  Here, the serial type ink jet recording apparatus has been described. However, the ink of the present invention is accumulated by recording the nozzles in an arbitrary arrangement such as a staggered pattern at a density equal to or about a fraction of the target image resolution. The present invention can also be applied to a recording apparatus having a so-called line head arranged more than the width of the medium.

  In addition, although it demonstrated in the example applied to the serial type (shuttle type) inkjet recording device which a carriage scans, it can apply similarly to the line type inkjet recording device provided with the line type head.

  Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be particularly preferably applied.

(Ink record)
The recorded matter recorded by the ink jet recording apparatus and the ink jet recording method of the present invention is the ink recorded matter of the present invention. The ink recorded matter of the present invention has an image formed on the recording medium using the recording ink of the present invention.
There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, special paper, cloth, a film, an OHP sheet etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
The ink recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Preparation Example 1)
[Preparation of yellow ink]
<Millbase prescription>
・ First Yellow 031 (manufactured by Dainichi Seika Co., Ltd., CI Pigment Yellow 74, added with 30% by weight of moisture) ... 18 parts by mass ・ Polyoxyethylene lauryl ether (nonionic surfactant) Agent) ... 5 parts by mass C ₁₂ H ₂₅ —O— (CH ₂ CH ₂ O) ₄₃ H
・ Ion exchange water: 77 parts by mass <ink formulation>
・ Mill base: 100 parts by mass ・ Glycerin: 10 parts by mass ・ 1,3-butanediol: 30 parts by mass ・ 2,2,4-trimethyl-1,3-pentanediol: 4 parts by mass Part ・ surfactant represented by the following structural formula: 4 parts by mass C ₁₃ H ₂₇ —O— (CH ₂ CH ₂ O) ₃ CH ₂ COONa
・ Proxel LV (antiseptic / antifungal agent) ・ ・ ・ 0.2 parts by mass ・ Ion-exchanged water ... 51.8 parts by mass

Next, when polyoxyethylene lauryl ether is dissolved in ion-exchanged water and the above pigments are mixed and sufficiently moistened, dyno mill KDL A type (manufactured by WAB) is filled with zirconia beads having a diameter of 0.5 mm as a kneading device. Then, kneading was performed at 2000 rpm for 2 hours to obtain a mill base.
Next, glycerin, 1,3-butanediol, 2,2,4-trimethyl-1,3-pentanediol, a surfactant represented by the above structural formula, and proxel LV are dissolved in ion-exchanged water to prepare a vehicle. After being prepared and mixed with the mill base, it was filtered through a Teflon (registered trademark) filter having an average pore diameter of 1 μm to obtain a yellow ink for inkjet recording having an average particle diameter of 75 nm. For the particle size measurement, a particle size measuring device (UPA150, manufactured by Microtrack Co., Ltd.) was used.

(Preparation Example 2)
[Preparation of magenta ink]
<Millbase prescription>
・ HOSTAFINE MAGENTA E-PT (Clariant Japan Co., Ltd., CI Pigment Red 122) 15 parts by mass ・ Polyoxyethylene lauryl ether (nonionic surfactant) represented by the following structural formula - 5 parts by weight _{C 12 H 25 -O- (CH 2} CH 2 O) 43 H
・ Ion exchange water: 80 parts by mass

  A mill base was produced in the same manner as the yellow ink of Preparation Example 1 using the above mill base formulation, and an magenta ink for inkjet recording having an average particle size of 120 nm was obtained using the same ink formulation as the yellow ink of Preparation Example 1. It was.

(Preparation Example 3)
[Preparation of cyan ink]
<Millbase prescription>
IRGALITE Blue 8700 (Ciba Specialty Chemicals Co., Ltd., CI Pigment Blue 15: 3) 13 parts by mass Polyoxyethylene lauryl ether represented by the following structural formula (nonionic surfactant) ) ... 5 parts by mass C ₁₂ H ₂₅ —O— (CH ₂ CH ₂ O) ₄₃ H
・ Ion exchange water: 82 parts by mass

  A mill base was produced by the same method as the yellow ink of Preparation Example 1 using the above mill base formulation, and a cyan ink for inkjet recording having an average particle size of 105 nm was obtained using the same ink formulation as the yellow ink of Preparation Example 1. It was.

Example 1
-Preparation of red ink-
<Millbase prescription>
-IRGZIN DPP Red BTR (Ciba Specialty Chemicals Co., Ltd., CI Pigment Red 254) ... 14 parts by mass-Polyoxyethylene lauryl ether represented by the following structural formula: 5 parts by mass C ₁₂ H ₂₅ —O— (CH ₂ CH ₂ O) ₄₃ H
・ Ion-exchanged water: 81 parts by mass <ink formulation>
・ Mill base: 100 parts by mass ・ Glycerin: 10 parts by mass ・ 1,3-butanediol: 30 parts by mass ・ 2-ethyl-1,3-hexanediol: 4 parts by mass Surfactant represented by the formula: 4 parts by mass C ₁₃ H ₂₇ —O— (CH ₂ CH ₂ O) ₃ CH ₂ COONa
・ Proxel LV (antiseptic / antifungal agent) ・ ・ ・ 0.2 parts by mass ・ Ion-exchanged water ... 51.8 parts by mass

Next, polyoxyethylene lauryl ether is dissolved in ion-exchanged water, and when the above pigment is mixed and sufficiently wetted, dyno mill KDL A type (manufactured by WAB) is filled with zirconia beads having a diameter of 0.5 mm as a kneading device. The mill base was obtained by kneading at 2000 rpm for 2 hours.
Next, glycerin, 1,3-butanediol, 2-ethyl-1,3-hexanediol, a surfactant represented by the above structural formula, and proxel LV are dissolved in ion-exchanged water to prepare a vehicle, After mixing with the mill base, the mixture was filtered through a Teflon (registered trademark) filter having an average pore diameter of 1 μm to produce a red ink having a volume average particle diameter of 156 nm.

  Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 1 was filled in the cartridge and set in the cyan ink place. For red, printing was performed using only all-dot (100%) red ink.

(Example 2)
-Preparation of red ink-
<Millbase prescription>
-IRGZIN DPP Red BTR (Ciba Specialty Chemicals Co., Ltd., CI Pigment Red 254) ... 14 parts by mass-Dispersant (anionic surfactant) represented by the following structural formula (A) ... 5 parts by mass
・ Ion exchange water: 81 parts by mass

  Next, the dispersant (anionic surfactant) represented by the structural formula (A) is dissolved in ion-exchanged water, and a mill base is produced in the same manner as in Example 1. The same ink as in Example 1 is used. A red ink having a volume average particle diameter of 102 nm was prepared using the formulation.

  Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 2 was filled in the cartridge and set in the cyan ink place. For red, printing was performed using only all-dot (100%) red ink.

(Example 3)
-Preparation of ink set-
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place.
Next, the red ink produced in Example 2 was filled in the cartridge and set in the place of the cyan ink. Red printing is performed at a recording duty of 50%, 90%, and 100%, and the ink ratio at each recording duty is 50% for red ink, 5% for red ink and 5% for yellow ink, and 100% for red ink at a recording duty of 90%. %, Recording duty 100%, red ink 95% and magenta ink 5%.

Example 4
-Preparation of green ink-
<Millbase prescription>
IRGALITE Green 6G (Ciba Specialty Chemicals Co., Ltd., CI Pigment Green 36) 15 parts by mass Dispersant (anionic surfactant) represented by the following structural formula (A) ..6 parts by mass
・ Ion exchange water: 79 parts by mass <ink formulation>
・ Mill base: 100 parts by mass ・ Glycerin: 15 parts by mass ・ 1,3-butanediol: 30 parts by mass ・ 2,2,4-trimethyl-1,3-pentanediol: 4 parts by mass Part ・ surfactant represented by the following structural formula: 4 parts by mass C ₁₃ H ₂₇ —O— (CH ₂ CH ₂ O) ₃ CH ₂ COONa
・ Proxel LV (antiseptic / antifungal agent) ・ ・ ・ 0.2 parts by mass ・ Ion-exchanged water ... 46.8 parts by mass

  Next, a mill base was produced by the same method as in Example 1 using the above mill base formulation, and a green ink having a volume average particle size of 123 nm was produced by the same method as in Example 1 using the above ink formulation.

  Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the cyan ink of Preparation Example 3 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the green ink produced in Example 4 was filled in a cartridge and set in a magenta ink place. For green, printing was performed using only all-dot (100%) green ink.

(Example 5)
<Millbase prescription>
· IRGALITE Green GFNP (Ciba Specialty Chemicals Co., Ltd., C.I Pigment Green 7.) ... 14 parts by weight dispersant represented by the following structural formula 5 parts by mass C ₁₂ H ₂₅ - O— (CH ₂ CH ₂ O) ₄₃ H
・ Ion-exchanged water: 81 parts by mass <ink formulation>
Millbase: 100 parts by mass Glycerin: 12 parts by mass Propylene glycol: 36 parts by mass 2-ethyl-1,3-hexanediol: 4 parts by mass Surfactant: 4 parts by mass C ₁₃ H ₂₇ —O— (CH ₂ CH ₂ O) ₃ CH ₂ COONa
・ Proxel LV (antiseptic / antifungal agent) ・ ・ ・ 0.2 parts by mass ・ Ion exchange water ... 43.8 parts by mass

When the dispersant represented by the structural formula is dissolved in ion-exchanged water, and the pigment is mixed and sufficiently wetted, a dyno mill KDL A type (manufactured by WAB) is used as a kneading device to add zirconia beads having a diameter of 0.5 mm. It was filled and kneaded at 2000 rpm for 2 hours to obtain a mill base.
Next, glycerin, propylene glycol, 2-ethyl-1,3-hexanediol, a surfactant represented by the above structural formula, and proxel LV were dissolved in ion-exchanged water to prepare a vehicle, which was mixed with the mill base. Thereafter, the mixture was filtered through a Teflon (registered trademark) filter having an average pore diameter of 1 μm to prepare a green ink for inkjet recording having an average particle diameter of 106 nm.

  Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place, and the above Example 5 The green ink produced in (1) was filled in the cartridge and set in the cyan ink place. For green, printing was performed using only all-dot (100%) green ink.

(Example 6)
<Millbase prescription>
- IRGALITE Green 6G (Ciba Specialty Chemicals Co., Ltd., C.I Pigment Green 36.) ... 14 parts by mass following structural dispersing agent represented by the formula 5 parts by mass C ₁₂ H ₂₅ - O— (CH ₂ CH ₂ O) ₁₁ —SO ₃ NH ₄
・ Ion-exchanged water: 81 parts by mass <ink formulation>
・ Mill base: 100 parts by mass ・ Glycerin: 14 parts by mass ・ 1,6-hexanediol: 32 parts by mass ・ 2-ethyl-1,3-hexanediol: 4 parts by mass ・ Pesresin A-520 (manufactured by Takamatsu Yushi Co., Ltd., water dispersible polyester resin, mass average molecular weight 14,000, solid content 30% by mass) 2.8 parts by mass FT-150 (manufactured by Neos Co., Ltd., the following structural formula (Fluorine-based surfactant represented by (16)) ... 4 parts by mass
In the structural formula (16), Rf1 is any one of the compounds represented by the following structural formulas (16a) and (16b).
・ Proxel LV (antiseptic / antifungal agent) 0.2 mass parts ・ Ion exchange water 43.0 mass parts

The dispersant represented by the structural formula was dissolved in ion-exchanged water, and a mill base was obtained in the same manner as in Example 5.
Next, glycerin, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, pesresin A-520, FT-150, and proxel LV are dissolved in ion-exchanged water to produce a vehicle, and mill base Then, the mixture was filtered through a Teflon (registered trademark) filter having an average pore diameter of 1 μm to obtain a green ink for inkjet recording having an average particle diameter of 99 nm.

  Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 are filled into a cartridge and set in a predetermined place. The cartridge was filled with the green ink and set in the place of cyan ink. For green, printing was performed using only all-dot (100%) green ink.

(Example 7)
<Millbase prescription>
IRGAZIN DPP Rubin TR (Ciba Specialty Chemicals Co., Ltd., CI Pigment Red 264) 15 parts by mass Dispersant represented by the following structural formula (17) 5 parts by mass
・ Ion-exchanged water: 80 parts by mass <ink formulation>
・ Mill base: 100 parts by mass ・ Glycerin: 15 parts by mass ・ 1,5-pentanediol: 30 parts by mass ・ 2,2,4-trimethyl-1,3-pentanediol: 4 parts by mass Parts FT-400SW (manufactured by Neos Co., Ltd., solid content 50 mass%, fluorine surfactant represented by the following structural formula (18)): 5 mass parts
In the structural formula (18), Rf1 represents any of the compounds represented by the structural formulas (16a) and (16b).
・ Proxel LV (antiseptic / antifungal) ... 0.2 parts by mass

The dispersant represented by the structural formula was dissolved in ion-exchanged water, and a mill base was obtained in the same manner as in Example 5.
Next, a vehicle is prepared by dissolving glycerin, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, FT-400SW, and proxel LV in ion-exchanged water, and mixed with the mill base. Then, the mixture was filtered through a Teflon (registered trademark) filter having an average pore diameter of 1 μm to prepare a red ink for inkjet recording having an average particle diameter of 87 nm.

  Next, using an ink jet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the cyan ink of Preparation Example 3 and the yellow ink of Preparation Example 1 are filled into a cartridge and set in a predetermined place. The filled red ink was filled in the cartridge and set in the place of magenta ink. For red, printing was performed using only all-dot (100%) red ink.

(Example 8)
<Millbase prescription>
・ IRGZAIN DPP Red BTR (Ciba Specialty Chemicals Co., Ltd., CI Pigment Red 254) 15 parts by mass Dispersant represented by the following structural formula (13) 6 parts by mass C ₁₂ H ₂₅ —O— (CH ₂ CH ₂ O) ₄₃ H
・ Ion exchange water: 79 parts by mass <ink formulation>
・ Milbase: 100 parts by mass ・ Glycerin: 12 parts by mass ・ Triethylene glycol: 32 parts by mass ・ 2,2,4-trimethyl-1,3-pentanediol: 4 parts by mass ・ PF -151N (manufactured by Omninova Solutions, fluorine-based surfactant represented by the following structural formula (19)): 2 parts by mass
In the Structural Formula (19), Rf is, CF _3, and represent any one of CF ₂ CF _3. n represents 8. m represents an integer of 20 or less. p represents an integer of 4 or less.
ACRYT WEM-321U (acrylic-urethane-core-shell type aqueous emulsion, self-crosslinking after printing, minimum film-forming temperature 10 ° C., average particle size 100 nm, solid content 38% by mass, acrylic / urethane ratio = 50/50, (Made by Taisei Kako Co., Ltd.) ... 7 parts by mass-Proxel LV (antiseptic / antifungal agent) ... 0.2 parts by mass-Ion exchange water ... 42.8 parts by mass

The dispersant represented by the structural formula was dissolved in ion-exchanged water, and a mill base was obtained in the same manner as in Example 5.
Next, glycerin, triethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, PF-151N, Acryte WEM-321U, and Proxel LV are dissolved in ion-exchanged water to produce a vehicle, and mill base And mixed with a 1 μm Teflon (registered trademark) filter to prepare a red ink for inkjet recording having an average particle size of 95 nm.

  Next, using an ink jet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the cyan ink of Preparation Example 3 and the yellow ink of Preparation Example 1 are filled into a cartridge and set in a predetermined place. The filled red ink was filled in the cartridge and set in the place of magenta ink. For red, printing was performed using only all-dot (100%) red ink.

Example 9
<Millbase prescription>
・ IRGZAIN DPP Red BTR (Ciba Specialty Chemicals, Inc., CI Pigment Red 254) 15 parts by mass Dispersant represented by the following structural formula (20) 6 parts by mass
・ Ion exchange water: 79 parts by mass <ink formulation>
・ Mill base: 100 parts by mass ・ Glycerin: 12 parts by mass ・ 3-Methyl-1,3-butanediol: 32 parts by mass ・ 2-Ethyl-1,3-hexanediol: 4 parts by mass Part · JC-05 (made by Seiko PMC Co., Ltd., styrene-acrylic copolymer, mass average molecular weight 20,000, solid content 21% by mass) ... 10 parts by mass · FT-110 (manufactured by Neos Co., Ltd., the following structure) Fluorine-based surfactant represented by formula (21)) 4 parts by mass
However, in the structural formula (21), Rf1 represents any of the compounds represented by the structural formulas (16a) and (16b).
・ Proxel LV (antiseptic / antifungal agent) ・ ・ ・ 0.2 parts by mass ・ Ion-exchanged water ... 37.8 parts by mass

The dispersant represented by the structural formula (20) was dissolved in ion-exchanged water, and a mill base was obtained in the same manner as in Example 5.
Next, glycerin, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, JC-05, FT-110, and proxel LV are dissolved in ion-exchanged water to prepare a vehicle. After mixing with the mill base, the mixture was filtered with a Teflon (registered trademark) filter having an average pore diameter of 1 μm to prepare a red ink for ink jet recording having an average particle diameter of 95 nm.

  Next, using an ink jet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the cyan ink of Preparation Example 3 and the yellow ink of Preparation Example 1 are filled into a cartridge and set in a predetermined place, and manufactured in Example 9 above. The filled red ink was filled in the cartridge and set in the place of magenta ink. For red, printing was performed using only all-dot (100%) red ink.

(Example 10)
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta of Preparation Example 2 and the yellow ink of Preparation Example 1 are filled into a cartridge and set in a predetermined location, and the red ink produced in Example 9 is used as the cartridge. And set in the place of cyan ink. Red printing is performed at a recording duty of 50%, 90%, and 100%, and the ink ratio at each recording duty is 50% for red ink, 5% for red ink and 5% for yellow ink, and 100% for red ink at a recording duty of 90%. %, Recording duty 100%, red ink 95% and magenta ink 5%.

(Example 11)
A recording ink was prepared by obtaining a mill base in the same manner as in Example 1 except that the dispersant of Example 1 was replaced with a lauryl ether sulfate Na salt represented by the following structural formula (22).
_{C 12 H 25 -O-SO 3} Na ··· structural formula (22)
Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 1 was filled in the cartridge and set in the place of the cyan ink. For red, printing was performed using only all-dot (100%) red ink.

(Example 12)
A mill base was prepared in the same manner as in Example 1 except that 2-ethyl-1,3-hexanediol in Example 1 was replaced with 3-methyl-2,4-heptanediol, and this was used for recording. An ink was prepared.
Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 1 was filled in the cartridge and set in the place of the cyan ink. For red, printing was performed using only all-dot (100%) red ink.

(Example 13)
A mill base was obtained in the same manner as in Example 1 except that N-methyl-2-pyrrolidone was used instead of glycerin and 1,3-butanediol in Example 1, and a recording ink was prepared.
Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 1 was filled in the cartridge and set in the place of the cyan ink. For red, printing was performed using only all-dot (100%) red ink.

(Example 14)
Example 6 except that Pesresin A-520 of Example 6 was replaced with Takeratta W-5025 (manufactured by Mitsui Takeda Chemical Co., Ltd., water-dispersible polyurethane resin, mass average molecular weight 18,000, solid content 30% by mass). In the same manner as above, a mill base was obtained to prepare a recording ink.
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the green ink produced in Example 6 was filled in the cartridge and set in the place of the cyan ink. For green, printing was performed using only all-dot (100%) green ink.

(Comparative Example 1)
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), fill the cartridge with the cyan ink of Preparation Example 3, the magenta ink of Preparation Example 2, and the yellow ink of Preparation Example 1, and set in a predetermined place for printing. Went.

(Comparative Example 2)
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 are filled into a cartridge and set in a predetermined place. The yellow ink of Preparation Example 1 and the Preparation Example A mixed red ink prepared by mixing two equal amounts of magenta ink was filled in a cartridge and set in a cyan ink place for printing.

(Comparative Example 3)
In Example 9, the mill base was the same as in Example 9 except that the pigment was changed to CROMOPHTAL Red A2B (Ciba Specialty Chemicals, Inc., CI Pigment Red 177, dianslaquinonyl red pigment). A red ink for inkjet recording having an average particle size of 106 nm was obtained using the formulation and the ink formulation.
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 9 was filled in the cartridge and set in the place of the cyan ink. For red, printing was performed using only all-dot (100%) red ink.

(Comparative Example 4)
To the millbase of Example 1, except that not put hexanediol to 2-ethyl-1,3, in the same manner as in Example 1, and the recording ink was prepared.
Next, using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place. Next, the red ink produced in Example 1 was filled in the cartridge and set in the place of the cyan ink. For red, printing was performed using only all-dot (100%) red ink.

(Comparative Example 5)
-Preparation of ink set-
Using an inkjet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), the magenta ink of Preparation Example 2 and the yellow ink of Preparation Example 1 were filled into a cartridge and set in a predetermined place.
Next, the red ink produced in Comparative Example 3 was filled in the cartridge and set in the place of the cyan ink. Red printing is performed at a recording duty of 50%, 90%, and 100%, and the ink ratio at each recording duty is 50% for red ink, 5% for red ink and 5% for yellow ink, and 100% for red ink at a recording duty of 90%. %, Recording duty 100%, red ink 95% and magenta ink 5%.

<Storage stability (viscosity)>
Table 1 shows the rate of change in viscosity (%) when each recording ink obtained in Examples 1 to 14 and Comparative Examples 1 to 5 was hermetically stored for one month in an environment of 50 ° C. The viscosity measurement was performed using a viscosity measuring device (manufactured by Toki Sangyo Co., Ltd., RC-500).

<Storage stability (particle size)>
Table 1 shows the change rate (%) of the average particle diameter when the recording inks obtained in Examples 1 to 14 and Comparative Examples 1 to 5 were hermetically stored for one month in an environment of 50 ° C. Show. For the particle size measurement, a particle size measuring device (UPA150, manufactured by Microtrack Co., Ltd.) was used.

<Discharge stability>
For each of the recording inks obtained in Examples 1 to 14 and Comparative Examples 1 to 5, an ink jet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.) is filled, and caps, cleaning, and the like are not performed during printer operation. The reliability was determined according to the following evaluation criteria based on how much time (seconds) the ejection direction shifted or the mass of the ejected droplets changed.
〔Evaluation criteria〕
○: 600 seconds or more Δ: 60 seconds or more, less than 600 seconds ×: less than 60 seconds

<Measurement of saturation and hue angle>
Using each recording ink, using the following plain paper as a print test paper, using an ink jet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.), performing solid printing in one pass, drying the lightness, It was measured with a reflection type color spectrophotometric densitometer (manufactured by X-Rite).
-Printing test paper-
Plain paper: My Paper SA (NBS Ricoh)
Plain paper: XEROX 4024 (Fuji Xerox Office Supply)
Plain paper: PB paper (Canon)

<Measurement of bidirectional color difference>
Using each recording ink, the following plain paper is used as a printing test paper, and an ink jet printer (IPSIO G707, manufactured by Ricoh Co., Ltd.) is used for two-way solid printing. After printing and drying, the brightness is reflected. It was measured with a type color spectrocolorimetric densitometer (manufactured by X-Rite). Table 1 shows the maximum value of the measured color difference.
-Printing test paper-
Plain paper: My Paper SA (NBS Ricoh)
Plain paper: XEROX 4024 (Fuji Xerox Office Supply)
Plain paper: PB paper (Canon)

* Since Comparative Example 1 is a comparative example in which a secondary color (yellow ink + magenta ink) forms red, viscosity change rate, particle size change rate, and ejection stability are not measured.

  The recording ink and ink set of the present invention are free of clogging of the head during recording, have excellent ejection stability, and provide a high-quality image with good color tone not only on dedicated recording paper but also on plain paper. However, it can be widely used as ink for general writing instruments such as water-based pens, water-based markers, water-based ballpoint pens, recorders, and pen plotters.

FIG. 1 is an external perspective view showing an example of an ink cartridge before being loaded into the recording apparatus of the present invention. FIG. 2 is a front sectional view of the ink cartridge of FIG. FIG. 3 is a schematic front view showing an example of a serial type ink jet recording apparatus equipped with an ink cartridge containing ink to which the present invention is applied. FIG. 4 is an external perspective view showing an example of a recording unit integrated with the recording head. FIG. 5A is a cross-sectional view of plain paper during forward recording (in order of C → Y) showing the state of ink droplets that have landed when ink droplets are ejected onto plain paper using the recording head. FIG. 5B is a cross-sectional view of plain paper during backward recording (in order of Y → C) showing the state of ink droplets that have landed when ink droplets are ejected onto plain paper using the recording head. FIG. 6 is a diagram illustrating an example of an ink recorded matter during backward recording in FIG. 5B. FIG. 7 is a graph showing the relationship between the recording duty and the color difference (ΔE *). FIG. 8A is a diagram for explaining a method of calculating the recording duty of a predetermined area of image data in the image area of the recording head. FIG. 8B is a diagram for explaining a scanning method in which the recording duty is calculated by shifting each window in units of one line in the scanning direction of the recording head. FIG. 8C is a diagram for explaining a scanning method in which the recording duty is calculated while being shifted for each window length in the band length direction. FIG. 9 is a flowchart for explaining the operation when calculating the recording duty of a predetermined area of the image data in the image area.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Side plate 2 Side plate 3 Main support guide rod 4 Sub support guide rod 5 Carriage unit 6 Head 6a Discharge surface (nozzle surface)
7 Ink Cartridge 7y Ink Cartridge 7m Ink Cartridge 7c Ink Cartridge 7k Ink Cartridge 8 Main Scanning Motor 9 Drive Pulley (Drive Timing Pulley)
10 Driven pulley (idler pulley)
DESCRIPTION OF SYMBOLS 11 Timing belt 12 Bottom plate 13 Sub frame 14 Sub frame 15 Conveyance roller 16 Paper 17 Sub scanning motor 18 Gear 19 Gear 21 Sub system 22 Cap means 23 Holder 24 Link member 25 Engagement part 26 Suction tube 27 Suction pump 28 Wiper blade 29 Blade Arm 30 Recording unit 31 Electrode 32 Nozzle 33 Ink tank 41 Cartridge body 42 Ink absorber 43 Case 44 Upper lid member 45 Ink supply port 46 Seal ring 47 Atmospheric release port 50 Cap member 55 Seal member A Space

Claims (18)

It contains at least a pigment, a dispersant, a water-soluble solvent, a penetrating agent, and water,
Wherein the pigment is viewed contains at least one of diketopyrrolopyrrole red pigment and phthalocyanine green pigment,
The penetrant contains a polyol compound having 8 to 11 carbon atoms,
The water-soluble solvent is glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, di- A recording ink characterized by being at least one selected from propylene glycol and trimethylolpropane . Diketopyrrolopyrrole-based red pigment, C. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264 and C.I. I. The recording ink according to claim 1, wherein the recording ink is at least one selected from CI Pigment Red 272.   A phthalocyanine green pigment is C.I. I. Pigment green 7 and C.I. I. The recording ink according to claim 1, which is at least one of pigment green 36. The recording ink according to any one of claims 1 to 3, wherein the dispersant is at least one of a compound represented by the following structural formula (11) and a compound represented by the following structural formula (12).
^{_{A 1 -O- (CH 2 CH 2}} O) k -SO 3 M 1 ··· structural formula (11)
However, the structural formula (11), A ¹ is branched optionally also an alkyl group having 8 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a benzyl group, styrenated phenol group, distyrenated phenol group , And a β-naphthyl group. k represents an integer of 5 to 30. M ¹ represents any ^one of an alkali metal, ammonium, phosphonium, and alkanolamine.
^{_{A 1 -O- (CH 2 CH 2}} O) i -H ··· structural formula (12)
However, the structural formula (12), A ¹ is branched optionally also an alkyl group having 8 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, a benzyl group, styrenated phenol group, distyrenated phenol group , And a β-naphthyl group. i represents an integer of 20 to 60.   The recording ink according to any one of claims 1 to 4, wherein the amount of the dispersant added is 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.   It contains an aqueous solution or dispersion of at least one of an acrylic resin, a methacrylic resin, a polyurethane resin, and a polyester resin, and the resin has a mass average molecular weight of 5,000 to 100,000 and an acid value. 6. The recording ink according to claim 1, wherein the recording ink is 50 to 200 KOH mg / g.   The mass (X) of the dispersant in the recording ink and the mass (Y) of the solid content of the aqueous solution or dispersion of at least one of the acrylic resin, methacrylic resin, polyurethane resin, and polyester resin, The recording ink according to claim 1, wherein the following formula, Y / X ≦ 1, is satisfied. A fluorosurfactant is contained, and the fluorosurfactant is at least one of perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, and perfluoroalkyl betaine. Item 8. The recording ink according to any one of Items 1 to 7. Polymer fine particles are contained, the volume average particle diameter of the polymer fine particles is 5 to 200 nm, and the polymer fine particles have a film forming property after printing on a recording medium, and the minimum film forming temperature is 30 ° C. or less. Item 9. The recording ink according to any one of Items 1 to 8. In an ink set comprising at least the recording ink according to any one of claims 1 to 9,
When recording red with a recording duty of 90% or more, when using red ink with a recording duty of 90% or more and magenta ink with a recording duty of less than 10%, and recording red with a recording duty of less than 90% An ink set comprising a combination of a red ink having a recording duty of 90% or more and a yellow ink having a recording duty of less than 10%. An ink cartridge comprising the recording ink according to claim 1 contained in a container. 10. An ink jet recording apparatus comprising at least ink flying means for recording an image by applying a stimulus to the recording ink according to claim 1 and causing the recording ink to fly. The inkjet recording apparatus according to claim 12, wherein the stimulus is at least one selected from heat, pressure, vibration, and light. 10. An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to the recording ink according to claim 1 and causing the recording ink to fly. 11. An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to each ink in the ink set according to claim 10 and causing each ink in the ink set to fly. The ink jet recording method according to claim 14, wherein the stimulus is at least one selected from heat, pressure, vibration, and light. When recording red with a recording duty of 90% or more, when using red ink with a recording duty of 90% or more and magenta ink with a recording duty of less than 10%, and recording red with a recording duty of less than 90% The inkjet recording method according to claim 14, wherein red ink having a recording duty of 90% or more and yellow ink having a recording duty of less than 10% are used in combination. An ink recorded matter comprising an image recorded using the recording ink according to any one of claims 1 to 9 on a recording medium.